Thermoplastic polymer fibers are frequently treated with fluorochemical compounds in order to affect the surface characteristics of the fiber, for example to improve water repellency or to impart stain or dry soil resistance. Most frequently, fluorochemical dispersions are applied topically to the fabrics made from these fibers by spraying, padding or foaming, followed by a drying step to remove water.
For example, a method is known for obtaining dry soil resistance and nonflame propagating characteristics in a textile fiber by applying topically aqueous dispersions of a variety of fluorinated esters derived from perfluoroalkyl aliphatic alcohols of the formula C.sub.n F.sub.2n+1 (CH.sub.2).sub.m OH where n is from about 3 to 14 and m is 1 to 3, together with mono- or polycarboxylic acids which contain from 3 to 30 carbons and can contain other substituents. The fluorinated esters include, among others, a perfluoroalkylethyl stearate corresponding to "ZONYL" FTS, as well as perfluoroalkylethyl diesters made from dodecanedioic acid or tridecanedioic acid.
It is well recognized that the process of manufacturing thermoplastic polymeric fibers and fabrics could be simplified and significant capital investment could be eliminated if the topical application were replaced by incorporating a fluorochemical additive into the polymer melt prior to the extrusion of the fiber. The difficulty has been in finding suitably effective fluorochemical additives.
Thermoplastic polymers include, among others, polyolefins, polyesters, polyamides and polyacrylates. Polyolefins, and in particular polypropylene, are frequently used for disposable nonwoven protective garments, particularly in the medical/surgical field, in part because of a polyolefin's inherent water-repellency. However, polyolefins are not inherently good repellents for other lower surface tension fluids frequently encountered in the medical field such as blood and isopropyl alcohol. To get around this deficiency, fluorochemical dispersions are applied topically to these fabrics.
The requirements of an additive suitable for incorporating into a polyolefin melt include, besides the ability to repel low surface tension fluids at a low concentration of the additive, a satisfactory thermal stability and low volatility to withstand processing conditions. Preferably the compound will migrate to the surface of the fiber so as to minimize the amount of additive needed for adequate repellency. While this migration can often be enhanced by post-extrusion heating of the fiber, it is more preferable for the migration to occur without the need for this heating step. This requirement for mobility in the polymeric fiber in turn tends to limit the size of the fluorochemical molecule, and effectively eliminates from consideration high molecular weight polymeric fluorochemical additives.
The general concept of incorporating fluorochemical additives into a polyolefin fiber melt is known, but the difficulty in finding suitable effective additives has limited the application of this concept. Many of the past efforts to evaluate such fluorochemical additives have been aimed at improving other properties of the polyolefin, and do not teach methods of its improving repellency to low surface tension fluids.
Nonwoven composite structures are known consisting in part of two or more melt-extruded nonwoven layers, at least one of which includes an additive which imparts to the surface at least one characteristic different than the surface characteristics of the polymer alone as a result of preferential migration of the additive to the surface without the need for post-formation treatment of any kind. Examples of the additive-including layer include polypropylene modified by commercially available fluorochemical additives, including "ZONYL" FTS defined above.
U.S. Pat. Nos. 5,178,931 and 5,178,932 disclose specific nonwoven laminiferous and composite structures respectively, consisting in part of three melt-extruded nonwoven layers, the second of which includes an additive which imparts alcohol repellency as a result of preferential migration of the additive to the surface without the need for post-formation treatment of any kind, and where at least one of the first and third layers has been treated by topical application of an agent to change its characteristics in some way. Examples of the additive-including second layer include commercially available fluorochemicals, including "ZONYL" FTS.
Soil resistant polymeric compositions are known which are prepared by melt extrusion with a nonpolymeric fluorochemical dispersed throughout the polymer. The polymers used include polypropylene, polyethylene, polyamide and polyester, and the fluorochemical used is a perfluoroalkylstearate, in particular "ZONYL" FTS.
In addition, a polymeric composition is known comprising a mixture of a polymer selected from the group of polypropylene, polyethylene, polyamide and polyester with a fluorochemical comprising a fluorinated oleophobic, hydrophobic alkyl group attached to a nonfluorinated oleophilic alkyl, aryl, aralkyl or alkaryl moiety optionally through a linking moiety, which can be melt extruded as a mixture. A more specific description of the above fluorochemical is not disclosed, but among the many compounds which are applicable are esters where the oleophilic organic group contains from 2 to 35 carbon atoms. Examples of such are "ZONYL" FTS or a product made by transesterifying "ZONYL" BA with methyl stearate and methyl palmitate.
An automotive coating film is known containing an organic solvent-soluble waxy hydrocarbon which possesses a fluorine-containing organic group. This component is a product obtained by esterifying and coupling a high molecular weight alcohol with a carboxylic acid which possesses a fluorine-containing group or a product obtained by esterifying and coupling a high molecular weight fatty acid and an alcohol which possesses a fluorine-containing group. As examples of high molecular weight alcohols included are those with average carbon chain lengths with up to 50 carbons. As examples of high molecular weight fatty acids included are those with carbon chain lengths of up to 31 carbons (mellisic acid). The products were tested only as a waxing agent for automobiles.
Japanese Patent Application 3-41160 to Kao Corp. teaches a thermoplastic resin composition containing a perfluoroalkyl group-containing long chain fatty ester of the formula R.sub.f --R.sub.1 --OCO--R.sub.2 where R.sub.f is a perfluoroalkyl group with 5 to 16 carbons, R.sub.1 is an alkylene group with 1 to 4 carbons, and R.sub.2 is an unsaturated alkyl group or a saturated alkyl group with 21 to 50 carbons. One example reacts C.sub.8 F.sub.17 C.sub.2 H.sub.4 OH with C.sub.27 H.sub.55 COOH to produce the ester. The resins included polyethylene and polypropylene. Benefits of the additive were shown by the contact angle of water with molded articles of the resin. No tests are reported on the repellency to low surface tension fluids of the resulting polymers.
In summary, while the prior art discloses numerous examples of polyolefin fibers containing a fluorochemical additive incorporated at the melt stage to alter the surface characteristics of the extruded fiber, much of this was aimed at soiling and staining resistance, water repellency or other purposes. Those references which were aimed at imparting alcohol repellency to polyolefin fabrics employ "ZONYL" FTS. A need exists to achieve superior repellency to low surface tension fluids and superior product efficiency. The fluorinated compounds of the present invention meet this need.